WO2015004444A1 - New cleaning formulation and method - Google Patents

New cleaning formulation and method Download PDF

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Publication number
WO2015004444A1
WO2015004444A1 PCT/GB2014/052079 GB2014052079W WO2015004444A1 WO 2015004444 A1 WO2015004444 A1 WO 2015004444A1 GB 2014052079 W GB2014052079 W GB 2014052079W WO 2015004444 A1 WO2015004444 A1 WO 2015004444A1
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WO
WIPO (PCT)
Prior art keywords
formulation
particles
cleaning
dosing
substrate
Prior art date
Application number
PCT/GB2014/052079
Other languages
English (en)
French (fr)
Inventor
Alan John Waddon
Robert Andrew BIRD
Stephen Derek Jenkins
Original Assignee
Xeros Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xeros Limited filed Critical Xeros Limited
Priority to EP14739525.5A priority Critical patent/EP3019585B1/en
Priority to CN201480039137.6A priority patent/CN105378048B/zh
Priority to KR1020167003483A priority patent/KR20160030290A/ko
Publication of WO2015004444A1 publication Critical patent/WO2015004444A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0082—Coated tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • This invention is concerned with the treatment of substrates using a formulation comprising solid cleaning particles and dosing particles.
  • the invention discloses a method which involves the dosing of additives during the treatment of the substrate using dosing particles mixed in with the solid cleaning particles, and a formulation for use in said method.
  • the dosing particles can comprise at least one releasable material comprising at least one cleaning and/or post-cleaning agent and/or other treatment additive.
  • the method is especially suited to providing substrates, such as laundry, which are especially clean and hygienic.
  • Aqueous cleaning processes are a mainstay of both domestic and industrial textile fabric washing. This washing generally comprises agitating fabrics in an aqueous solution of detergent, often at elevated temperatures. Supplemental additives, such as fabric conditioners, dye transfer inhibitors, anti-redeposition agents, perfumes or products for enhancing hygiene are customarily added as separate dosing operations, often with the detergent.
  • washing processes whether involving domestic washing machines or their industrial equivalents (usually referred to as washer extractors), involve aqueous submersion of fabrics followed by soil removal, aqueous soil suspension, and water rinsing.
  • Higher levels of energy (or temperature), water and detergent usually result in better cleaning.
  • the water usage level strongly influences the mechanical action of the process on the fabric, which is another significant performance parameter; this is the agitation of the cloth surface during washing, which plays a key role in releasing embedded soil.
  • WO-A-2007/128962 discloses a method and formulation for cleaning a soiled substrate, which greatly reduces the usage of water, energy and detergent while still providing the mechanical action necessary for cleaning.
  • the method comprises the treatment of the moistened substrate with a formulation comprising a multiplicity of polymeric particles, wherein the formulation is free of organic solvents.
  • the substrate is wetted so as to achieve a substrate to water ratio of between 1 :0.1 to 1 :5 w/w
  • the formulation additionally comprises at least one cleaning material, which typically comprises a surfactant, which most preferably has detergent properties.
  • the substrate comprises a textile fibre and the polymeric particles may, for example, comprise polyamide, polyester, polyalkene, polyurethane or a copolymer thereof, but are most preferably in the form of nylon beads.
  • WO-A- 2012/056252 describes a method for the most efficient use and removal of such polymeric particles in a cleaning process, and WO-A-2012/095677 extends this method to the use of non-polymeric cleaning particles, and mixtures of non-polymeric and polymeric cleaning particles.
  • a further apparatus which facilitates efficient separation of cleaning particles from the cleaned substrate at the conclusion of the cleaning operation, and which comprises a perforated drum and a removable outer drum skin which is adapted to prevent the ingress or egress of fluids and solid particulate matter from the interior of the drum, the cleaning method requiring attachment of the outer skin to the drum during a wash cycle, after which the skin is removed prior to operating a separation cycle to remove the cleaning particles, following which the cleaned substrate is removed from the drum.
  • the cleaning parts of the formulation are added before or during the main wash cycle in order to provide the degree of stain removal required, whilst the remaining, more expensive - and hence more value adding - parts of the formulation are added as a post-treatment, usually during rinsing, following removal of the polymeric particles from the wash process.
  • the cleaning components comprise surfactants, enzymes and oxidising agents or bleaches
  • the post-treatment components include, for example, anti-redeposition agents, perfumes and optical brighteners. Addition of the cleaning and post- treatment components in this way allows further reduction in levels of use, and hence significant cost savings in comparison to conventional all-in-one detergent formulations.
  • a cartridge dosing system as described in WO-A-201 1/128676 may also be used for this purpose.
  • each detergent component is typically concentrated such that a number of dosages are contained within the cartridge, these being used up gradually over a number of wash cycles.
  • the cartridge itself and the docking system for insertion into the cleaning apparatus can, however, be complex in construction, and hence costly.
  • the inventors provide a process which addresses the difficulties of dilution and transport of detergent components as hereinbefore described.
  • dosing particles which release additives over a wash cycle for use in conjunction with the solid cleaning particles.
  • the dosing particles can contain the detergent components preferred for effective cleaning and post treatment and, as they are intimately mixed with the solid cleaning particles, they are carried directly to the fabric surface, thereby delivering the detergent components to the washload in the most targeted way possible.
  • the dosing particles can contain the detergent components preferred for effective cleaning and post treatment and, as they are intimately mixed with the solid cleaning particles, they are carried directly to the fabric surface, thereby delivering the detergent components to the washload in the most targeted way possible.
  • the present invention also envisages the dosing of other beneficial additives via the dosing particles.
  • beneficial additives include the addition of antimicrobial agents in order to sterilise the fabric, or of boosted levels of optical brightening agents, anti-redeposition agents, fragrances or dye transfer inhibitors.
  • the benefit of the dosing particle is its direct and targeted delivery of the specific additive to the fabric surface by a particularly elegant and effective means, i.e. in admixture with the solid cleaning particles.
  • WO-A- 2011/150138 discloses encapsulated, solid, water soluble benefit agents and products comprising such encapsulates, as well as processes for making and using the encapsulates and products.
  • a melamine formaldehyde and/or urea formaldehyde encapsulation process is described.
  • US-A-2004/242133 teaches an abrasive cleaning article comprising spread abrasive particles and microencapsulated particles of a perfumed substance contained in urea-formaldehyde walls bonded to a three-dimensional non-woven fibre web by a resin adhesive and also refers to a process for the production process of the abrasive cleaning article.
  • US-A-201 1/245136 is concerned with encapsulated, solid, water soluble benefit agents and products comprising such encapsulates, in addition to processes for making and using the encapsulates and products.
  • the disclosed invention seeks, by employing a protective suspension agent, to overcome emulsification problems and to minimise negative interactions between the benefit agents and shell materials that occur during particle production and processing.
  • WO- A-2010/079466 relates to encapsulated benefit agents, compositions comprising such encapsulated benefit agents, and processes for making and using the compositions. Disadvantages associated with prior art encapsulated benefit agents are eliminated or minimised so as to provide, for example, enhanced perfume delivery.
  • GB-A-2432844 describes polymer particles which comprise a perfume, a polymer and a cationic deposition aid which are delivered to fabric during laundering and provide long lasting adherence of the perfume to the fabric.
  • a method of depositing perfume onto a substrate via such a composition is also disclosed.
  • the particle optionally has a core/shell morphology and is prepared using miniemulsion polymerisation.
  • the polymer of the particle is preferably butyl methacrylate, and a shell layer of vinyl acetate is optionally present; the cationic deposition aid may be a cationically modified cellulose or guar gum.
  • a laundry additive particle having multiple coatings, together with compositions comprising such particles.
  • the particle comprises a central core comprising a porous carrier core material and a glassy encapsulating material intermixed with the carrier material.
  • the encapsulating material is derived from at least partially water-soluble hydroxylic compounds and an external coating material is coated on the core particle to provide a substantially non-tacky surface.
  • the external coating material is derived from at least partially wash soluble or dispersible compounds selected from waxes, water-soluble polymers, fatty compounds, carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and chitosan, and mixtures thereof.
  • a laundry or cleaning agent such as a perfume is preferably supported on or contained in the porous carrier.
  • the present invention thereby addresses, at least in part, one or more of the following technical problems:
  • a formulation comprising a multiplicity of solid cleaning particles and a multiplicity of dosing particles, wherein said dosing particles comprise core-shell particles comprising at least one host material and at least one releasable material, wherein said host material comprises, as the shell of the dosing particles, at least one partially or completely water soluble polymeric material, and said at least one releasable material comprises the core material of the dosing particles, comprising at least one cleaning or post-cleaning agent or other treatment additive for the treatment of a substrate.
  • the dosing particles comprise two or more releasable materials selected from any of the combinations of at least one cleaning agent, at least one post-cleaning agent and at least one other treatment additive.
  • Said shell material provides, inter alia, mechanical integrity to the particles and facilitates efficient handling and delivery of the particles.
  • the solid cleaning particles may comprise polymeric and/or non-polymeric cleaning particles.
  • Solid polymeric cleaning particles are typically substantially ellipsoidal, cylindrical or spherical in shape, typically having an average density in the range of 0.5-2.5 g/cm 3 and typically having an average volume in the range of 5-275 mm 3 .
  • said formulation is used for the cleaning of soiled substrates and said at least one releasable material comprises at least one cleaning agent.
  • said at least one releasable material comprises at least one cleaning agent, most particularly at least one detergent, which typically comprises at least one surfactant.
  • said at least one releasable material additionally or solely comprises at least one post-cleaning agent.
  • said cleaning agents and post-cleaning agents are especially cleaning chemicals or post-cleaning chemicals which are typically components of the detergent formulation used in a wash process.
  • Cleaning agents are, therefore, typically surfactants, enzymes, oxidising agents or bleaches
  • suitable post-cleaning agents include, but are not limited to, optical brightening agents, anti-redeposition agents, dye transfer inhibition agents and fragrances.
  • Said host material comprises a non-active polymeric or non-polymeric material which serves to transport the releasable material to the washload surface in a controlled manner but plays no active part in the cleaning process.
  • Various materials may be employed for this purpose including, for example, polymeric materials such as polyvinyl alcohol) (PVOH), copolymers of polyvinyl alcohol) and polyvinyl acetate), poly(ethyl vinyl alcohol) (EVOH), hydroxypropylmethylcellulose (HPMC), cellulose, starch, hydroxypropylcellulose (HPC), hydroxyethylcellulose (HEC), carboxymethyl cellulose (CMC), polyvinyl pyrrolidinone) (PVP), poly(ethylene glycol) (PEG) and gelatin, or salts thereof.
  • PVOH polyvinyl alcohol
  • EVOH ethyl vinyl alcohol
  • HPMC hydroxypropylmethylcellulose
  • HPMC hydroxypropylmethylcellulose
  • HPC hydroxypropylcellulose
  • Typical polyvinyl alcohols) for use in the present invention have a degree of hydrolysis of from 50 to 99%, more typically from 70 to 98%, and even more typically from 80 to 97%. The percentage is typically expressed as a molar percentage. Polyvinyl alcohol) having a degree of hydrolysis of 94% is typically suitable for the purposes of the invention. The degree of hydrolysis has an effect on the release rate of the releasable material. The typical degrees of hydrolysis correspond to the best release profile. Poly(ethylene glycol) (PEG) has also been found to be an especially suitable host material.
  • Said dosing particles are typically used and consumed in a single substrate treatment operation.
  • Said dosing particles may be obtained by means of any of the standard preparative methods for core-shell particles which are available and well known in the art, and which typically involve the coating of the core (releasable) material with the shell (host) material using any of a number of standard coating methods.
  • the core is formed from powders or mixtures of powders comprising the cleaning or post-cleaning agent or other treatment additive and these materials are compressed under pressure to form a solid tablet by means of procedures which are well known in, for example, the pharmaceutical industry.
  • the shell is conveniently formed on the core by coating the core with a solution of the host material by spray coating the solution onto the core or, alternatively, by dipping the core into the solution and then drying the particles; again, such techniques are well known in, for example, the pharmaceutical industry.
  • the core material is soluble in water
  • the shell is applied as a solution of shell material in an organic liquid, optionally at ambient or elevated temperatures.
  • One suitable organic liquid is ethanol, especially when the shell material is poly(ethylene glycol).
  • Solid polymeric cleaning particles may comprise either foamed or unfoamed polymeric materials.
  • the polymeric particles may comprise polymers which are either linear or crosslinked.
  • Solid polymeric cleaning particles preferably comprise polyalkenes such as polyethylene and polypropylene, polyamides, polyesters or polyurethanes.
  • polyalkenes such as polyethylene and polypropylene, polyamides, polyesters or polyurethanes.
  • said polymeric particles comprise polyamide or polyester, most particularly nylon, polyethylene terephthalate or polybutylene terephthalate, often in the form of beads.
  • Said polyamides and polyesters are found to be particularly effective for aqueous stain/soil removal, whilst polyalkenes are especially useful for the removal of oil-based stains.
  • copolymers of the above polymeric materials may be included in said polymeric cleaning particles.
  • the properties of the polymeric materials may be tailored to specific requirements by the inclusion of monomeric units which confer particular properties on the copolymer.
  • the copolymers may be adapted to attract particular staining materials by comprising monomers which, inter alia, are ionically charged, or include polar moieties or unsaturated organic groups.
  • Suitable solid non-polymeric cleaning particles may comprise particles of glass, silica, stone, wood, or any of a variety of metals or ceramic materials.
  • Suitable metals include, but are not limited to, zinc, titanium, chromium, manganese, iron, cobalt, nickel, copper, tungsten, aluminium, tin and lead, and alloys thereof.
  • Suitable ceramics include, but are not limited to, alumina, zirconia, tungsten carbide, silicon carbide and silicon nitride.
  • Each of said solid non-polymeric cleaning particles is typically substantially ellipsoidal, cylindrical or spherical in shape and typically has an average density in the range of 3.5-12.0 g/cm 3 and typically has an average volume in the range of 5-275 mm 3 .
  • a mixture of polymeric and non-polymeric solid cleaning particles can be used.
  • a method for the treatment of a substrate comprising the treatment of the substrate with a formulation according to the first aspect of the invention.
  • the method of the invention is typically carried out in an aqueous environment and, more typically, in the presence of limited quantities of water.
  • the amount of water present during the performance of the method of the invention is far less than in the case of the methods of the prior art, thereby providing one of the principal benefits associated with said method.
  • water is generally added so as to achieve a water to substrate ratio which is typically between 2.5: 1 and 0.1 : 1 w/w.
  • said treatment method comprises a method for the cleaning of a soiled substrate and typically, therefore, said at least one releasable material comprises at least one cleaning agent, most particularly at least one detergent, which typically comprises at least one surfactant.
  • said at least one releasable material additionally or solely comprises at least one post-cleaning agent and/or at least one other treatment additive.
  • said releasable materials are typically delivered directly to the substrate surface by means of controlled localised release from dosing particles containing these agents.
  • the cleaning and post-cleaning agents, and/or other treatment additives are delivered in the most targeted manner possible, thereby reducing the amount of releasable material required to achieve the desired cleaning, post-cleaning or treatment effect.
  • the release of said releasable material from the dosing particle may be controlled by selection of a suitable host material as previously indicated, such that it completely releases in one wash cycle.
  • Polymeric or non-polymeric solid cleaning particles, or mixtures thereof, are typically added at a particle to substrate addition level of 0.1 : 1-30: 1 by dry mass of substrate (washload).
  • the substrate treated by the claimed method may comprise any of a wide range of substrates, including, for example, plastics materials, leather, paper, cardboard, metal, glass or wood.
  • said substrate most preferably comprises a textile fibre, which may be either a natural fibre, such as cotton, or a synthetic textile fibre, for example nylon 6,6 or a polyester, or a blend of natural and synthetic fibres.
  • the dosing particles are typically added at a ratio from 0.1-50.0% w/w of the total mass of the cleaning particle formulation.
  • Each of said dosing particles is typically substantially cylindrical or spherical in shape and typically has an average density in the range of 0.5-2.5 g/cm 3 and typically has an average volume in the range of 5-500 mm 3 .
  • the dosing particles have an average volume in the range of from 5- 5000 mm 3 .
  • FIG. 1 For embodiments of the invention envisage a method for the treatment of a substrate wherein the surface of a substrate is treated with a post-cleaning agent, the method comprising treating the substrate with a multiplicity of solid cleaning particles and a multiplicity of dosing particles, wherein said dosing particles comprise additives which are free from cleaning agents.
  • Said embodiments are again carried out in the presence of wash water, and involve the use of dosing particles containing post-cleaning agents. Examples of such embodiments may, for example, involve dosing with an optical brightening agent, an anti-redeposition agent, a fragrance, or a dye transfer inhibition agent.
  • a third aspect of the invention provides a method for the cleaning of a cleaning apparatus, said method comprising the treatment of the internal systems of the apparatus with a formulation comprising a multiplicity of solid cleaning particles and a multiplicity of dosing particles, wherein said dosing particles comprise at least one host material and at least one releasable material, wherein said host material comprises, as the shell of the dosing particles, at least one partially or completely water soluble polymeric material and said at least one releasable material comprises the core material of the dosing particles, comprising an antimicrobial agent.
  • the formulation is circulated such that the antimicrobial agent is released within the washing apparatus internal water storage areas or conduits during idle periods between wash cycles, thereby enhancing the hygiene of the apparatus itself.
  • the wash system provided by the present invention is designed to improve mechanical interaction between all of the particles of the cleaning formulation and the fabrics, and facilitates the easy removal of the solid cleaning particles from the fabrics after the cleaning or other post-cleaning process is complete, thereby facilitating their re-use in subsequent processes according to the method.
  • the invention is not limited to procedures for cleaning, post-cleaning and other treatments of fabrics, and is applicable to any solid particle cleaning process, such as dish washing or carpet cleaning.
  • dosing particles in the absence of solid cleaning particles is significantly less effective and, whilst not wishing to be limited by theory, it is considered that this is because the physical action of the solid cleaning particles enhances the disintegration of the dosing particles, the release of the releasable material, the dispersal of the releasable material throughout the washload, and the penetration of the releasable material into the fibres of fabrics and textiles.
  • Figure 1 is a graph illustrating the effect of the quantity of Dosing Particles according to the invention on measured values of a* using a 1.4 kg washload ;
  • Figure 2 is a graphical representation of the effect of the quantity of Dosing Particles according to the invention on measured values of L* for a 1.4 kg washload
  • Figure 3 shows a graph which illustrates the effect of the quantity of Dosing Particles according to the invention on measured values of b* for a 1.4 kg washload;
  • Figure 4 is a graph which shows DE Values observed after washing according to the invention for a 1.4 kg washload
  • Figure 5 provides a photographic illustration of cloths washed according to various procedures
  • Figure 6 is a graphical representation of the effect on Dye Transfer Inhibition performance of variations in the weight of Dye Eluting Material and of Chitosan Core-Shell Particles in the wash;
  • Figure 7 is a graph showing how the use of Core-Shell Dosing Particles with
  • Figure 8 is a photograph showing residual powder on a cotton fabric.
  • Figure 9 is a photograph which shows the powder recovered from the washing machine.
  • the first aspect of the invention envisages a formulation comprising a multiplicity of solid cleaning particles and a multiplicity of dosing particles, wherein said dosing particles comprise at least one host material and at least one releasable material, as hereinbefore defined.
  • the cleaning agents dosed by the dosing particles comprise surfactants, enzymes, oxidising agents and bleach, whilst the post-cleaning agents include, for example, optical brightening agents, anti-redeposition agents, dye transfer inhibition agents and fragrances.
  • the cleaning agents may optionally also include, for example, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal agents and suds suppressors.
  • Suitable surfactants may be selected from non-ionic and/or anionic and/or cationic surfactants and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.
  • the surfactant is typically present at a level of from about 0.1 %, from about 1 %, or even from about 5% w/w of the dosing particle mass up to about 99.9%, to about 80%, to about 35%, or even to about 30% w/w of the dosing particle mass, or any of the ranges defined thereby.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, other cellulases, other xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, [beta]- glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, mannanase and amylases, or mixtures thereof.
  • a typical combination may comprise a mixture of enzymes such as protease, lipase, cutinase and/or cellulase in conjunction with amylase.
  • enzyme stabilisers may also be included amongst the cleaning agents.
  • enzymes for use in detergents may be stabilised by various techniques, for example by the incorporation of water-soluble sources of calcium and/or magnesium ions in the compositions.
  • bleach compounds include, but are not limited to, peroxygen compounds, including hydrogen peroxide, inorganic peroxy salts, such as perborate, percarbonate, perphosphate, persilicate, and mono persulphate salts (e.g. sodium perborate tetrahydrate and sodium percarbonate), and organic peroxy acids such as peracetic acid, monoperoxyphthalic acid, diperoxydodecanedioic acid, N,N'-terephthaloyl- di(6-aminoperoxycaproic acid), ⁇ , ⁇ '-phthaloylaminoperoxycaproic acid, phthalimido peroxy hexanoic acid and amidoperoxyacid.
  • peroxygen compounds including hydrogen peroxide, inorganic peroxy salts, such as perborate, percarbonate, perphosphate, persilicate, and mono persulphate salts (e.g. sodium perborate tetrahydrate and sodium percarbonate), and organic peroxy acids such as peracetic acid
  • Percarbonates, and especially sodium percarbonate are particularly preferred bleach compounds.
  • Bleach activators include, but are not limited to, carboxylic acid esters such as sodium nonanoyloxybenzene sulfonate.
  • Other bleach activators include tetraacetylethylenediamine (TAED).
  • TAED is especially preferred as a bleach activator.
  • percarbonate/TAED combinations are especially preferred as they can provide substrates (such as textiles and fabrics) which are more hygienic.
  • hygienic it is preferably meant that the treated substrate has less bacteria, for example at least 1000x, at least 10,000x, at least 100,000x or even at least 1 ,000,000x less bacteria when compared to the untreated substrate.
  • Log kills which equate to Log 3, 4, 5 and 6 kills of bacteria.
  • Log 5 and Log 6 kills are especially difficult to achieve without using high (>60°C) temperatures and/or high loadings of hypochlorite.
  • this can be achieved by a treatment according to the method of the invention at a temperature of less than 50°C, at a temperature of less than 45°C, at a temperature of less than 40°C or even at a temperature of less than 35°C.
  • the temperature of the treatment is more than 0°C, more typically more than 10°C.
  • Such a treatment offers substantial energy savings and provides for good fabric/textile fibre care as compared to chlorine-based bleach chemicals which tend to slowly damage the fabric/textile fibres and which are more harmful to the environment.
  • the dosing particles comprise at least one releasable material comprising at least one bleach compound, which is preferably a percarbonate, more preferably sodium percarbonate.
  • the dosing particles comprise a bleach activator, which is preferably tetraacetylethylenediamine (TAED).
  • TAED tetraacetylethylenediamine
  • the dosing particles comprise both a bleach compound (as preferred above) and a bleach activator (as preferred above).
  • one dosing particle comprises a bleach compound (as preferred above) and another dosing particle comprises a bleach activator (as preferred above).
  • the typical weight ratio of bleach compound to bleach activator is from 10: 1 to 1 : 10; more typically from 5:1 to 1 :5; even more typically from 3:1 to 1 :3; yet more typically from 2: 1 to 1 :2.
  • the amounts of bleach compound and bleach activator used in the method according to the present invention typically provide the abovementioned preferred weight ratios.
  • Suitable builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicates, polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and
  • One or more copper, iron and/or manganese chelating agents and/or one or more dye transfer inhibiting agents may also be included.
  • Suitable dye transfer inhibiting agents include chitosan, polyvinylpyrrolidone polymers (crosslinked or uncrosslinked), polyamine N-oxide polymers, polyvinyloxazolidones, polyvinylimidazoles, salts of all these polymers, sodium bentonite, calcium bentonite, montmorillionite, kaolinite, kaoline, or mixtures thereof.
  • Especially suitable examples of dye transfer inhibiting agents are copolymers of N-vinylpyrrolidone and N-vinylimidazole.
  • the cleaning agents can also optionally contain dispersants.
  • Suitable water- soluble organic dispersants are homo- or co-polymeric polycarboxylic acids, or their salts, in which the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • post-cleaning anti-redeposition agents include, but are not limited to, carboxymethylcellulose (CMC), polyacrylates and polyethylene glycol (PEG), or salts thereof. Of these, carboxymethylcellulose and salts thereof, e.g. the sodium salt thereof, are especially suitable.
  • Suitable post-cleaning fragrances include, but are not limited to, multi-component organic chemical formulations which can contain alcohols, ketones, aldehydes, esters, ethers and nitrile alkenes, and mixtures thereof.
  • Suitable post-cleaning optical brightening agents include, but are not limited to, several organic chemical classes, of which the most popular are stilbene derivatives, whilst other suitable classes include benzoxazoles, benzimidazoles, 1 ,3-diphenyl-2-pyrazolines, coumarins, 1 ,3,5-triazin-2-yls and naphthalimides.
  • Examples of such compounds include, but are not limited to, 4,4'-bis[[6-anilino-4(methylamino)-1 ,3,5-triazin-2-yl]amino]stilbene- 2,2'-disulfonic acid, 4,4'-bis[[6-anilino-4-[(2-hydroxyethyl)methylamino]-1 ,3,5-triazin-2- yl]amino]stilbene-2,2'- disulphonic acid, disodium salt, 4,4'-bis[[2-anilino-4-[bis(2- hydroxyethyl)amino]-1 ,3,5-triazin-6-yl]amino]stilbene-2,2'-disulfonic acid, disodium salt, 4, 4'-bis[(4,6-dianilino-1 ,3, 5-triazin-2-yl)amino]stilbene-2, 2 -disulphonic acid, disodium salt, 7-diethylamino-4-
  • antimicrobial agents suitable examples of which include, but are not limited to, hexadecyltrimethylammonium bromide (CTAB), ionic silver containing zeolites, benzalkonium choride, Triclosan ® and silver nitrate.
  • CTAB hexadecyltrimethylammonium bromide
  • ionic silver containing zeolites e.g., zeolites
  • Triclosan ® e.g., Triclosan ®
  • silver nitrate e.g., hexadecyltrimethylammonium bromide (CTAB), ionic silver containing zeolites, benzalkonium choride, Triclosan ® and silver nitrate.
  • the antimicrobial agent may also be generated in situ.
  • at least one of the antimicrobial precursors is in the dosing particles as the releasable material.
  • all of the components needed to generate the antimicrobial compounds
  • the dosing particles comprise a host material comprising a shell comprising polyvinyl alcohol) (PVOH), copolymers of polyvinyl alcohol) and polyvinyl acetate), hydroxypropylmethylcellulose (HPMC), lactose, cellulose, starch, hydroxypropylcellulose (HPC), hydroxyethylcellulose (HEC), polyvinyl pyrrolidinone) (PVP), crosslinked PVP, poly(ethylene glycol) (PEG) and gelatin.
  • PVOH polyvinyl alcohol
  • HPMC hydroxypropylmethylcellulose
  • HPMC hydroxypropylmethylcellulose
  • HPC hydroxypropylcellulose
  • HEC hydroxyethylcellulose
  • PVP polyvinyl pyrrolidinone
  • the host material comprising the shell is comprised of one or more partially or completely water soluble polymeric materials.
  • the host material comprising the shell comprises no water-insoluble polymeric materials.
  • the solid cleaning and dosing particles are of such a shape and size as to allow for good flowability and intimate contact with a soiled substrate, which typically comprises a textile fabric.
  • said particles typically comprise cylindrical or spherical beads; other shapes are possible, such as ellipsoidal, cuboid, etc.
  • the combination of particle size, shape and density is such that the mechanical interaction of the particle with the fabric is optimised, it being sufficiently vigorous to provide effective cleaning but, at the same time, uniform and gentle enough to reduce fabric damage when compared with conventional aqueous processes.
  • the uniformity of the mechanical action generated by the chosen particles across the entire fabric surface that is the key factor in this regard.
  • Such uniform mechanical action is also the key to localised and controlled application of the cleaning agents, post-cleaning agents and other treatment additives from the dosing particles across the entire substrate surface.
  • the particle parameters are also controlled so as to allow for easy separation of the particles from the washload at the end of the wash process.
  • particle size and shape may be controlled in order to minimise entanglement with the substrate, and the combination of suitable particle density and high free volume (ullage) in the washing machine tumbling process together promote particle removal. This is especially relevant in the case of fabric treatment processes.
  • the solid cleaning particles typically have an average particle size of from 1 to 100 mm, more typically from 1 to 50 mm; even more typically from 1 to 15 mm, yet more typically from 2 to 10 mm and most typically from 3 to 6 mm.
  • the size is typically the longest linear size measurable.
  • the dosing particles typically have a particle size of from 1 to 100 mm; more typically from 5 to 50 mm.
  • the dosing particles typically have a weight of from 1 to 50 g, more typically from 1 to 30 g and most typically from 5 to 30 g.
  • the dosing particles typically contain less than 5 wt%, more typically less than 1 wt% of liquid components, and most typically are substantially free of such liquid components.
  • the weight ratio of solid cleaning particles to dosing particles is from 100,000:1 to 1 : 1 , more typically from 10,000:1 to 10: 1 and most typically from 10,000:1 to 100: 1
  • the ratio of solid cleaning particles to substrate is generally in the range of from 30:1 to 0.1 :1 w/w (dry mass of substrate (washload)), preferably in the region of from 10: 1 to 1 : 1 w/w, with particularly favourable results being achieved with a ratio of between 5:1 and 1 :1 w/w, and most particularly at around 2:1 w/w.
  • 10 g of solid cleaning particles would be employed, and therefore up to a further 5 g of dosing particles would be used in addition to dose cleaning and post-cleaning agents, and other treatment additives.
  • water is added to the system.
  • a soiled substrate may be moistened by wetting with mains or tap water prior to loading into a cleaning apparatus.
  • water is added to the process such that the washing treatment is carried out so as to achieve a water to substrate ratio which is typically between 2.5: 1 and 0.1 : 1 w/w; more frequently, the ratio is between 2.0:1 and 0.8: 1 , with particularly favourable results having been achieved at ratios such as 1.5: 1 , 1.2:1 and 1.1 : 1.
  • the method of the invention finds particular application in the cleaning of textile fibres and fabrics.
  • the conditions employed in such a cleaning system are very much in line with those which apply to the conventional wet cleaning of textile fibres and, as a consequence, are generally determined by the nature of the fabric and the degree of soiling.
  • typical procedures and conditions are in accordance with those which are well known to those skilled in the art, with fabrics generally being treated according to the method of the invention at, for example, temperatures of between 5 and 95°C, typically for a duration of between 10 minutes and 1 hour, then optionally being rinsed in water and dried.
  • the release of additives from the dosing particles is controlled such that these release completely in one wash. This can provide increased convenience for the user.
  • the localised delivery of cleaning and post-cleaning agents, and other treatment additives, to the fabric surface by the dosing particles is the predominant feature that ensures excellent cleaning and post-cleaning performance. No problems are observed with solid cleaning or dosing particles adhering to the fibres at the conclusion of the cleaning operation, and all particles may subsequently be removed from the substrate of the washload.
  • the method of the invention may particularly advantageously be carried out by using, for example, cleaning apparatus as disclosed in WO-A-2010/094959, WO-A- 2011/064581 and especially WO-A-201 1/098815.
  • the solid cleaning particles are re-used in further procedures according to the method of the present invention.
  • the dosing particles are typically consumed in a single wash and are not usually available for re-use.
  • Further embodiments of the invention envisage a method for treating the surface of a substrate with an additive, the method comprising treating the soiled substrate with solid cleaning particles and wash water, and mixing in additional dosing particles containing an appropriate treatment additive.
  • Suitable examples could include the release of an antimicrobial agent onto a fabric surface for sterilisation purposes.
  • the method typically comprises treating the soiled substrate with solid cleaning particles and wash water, and mixing in dosing particles containing an appropriate post-cleaning agent or treatment additive, wherein the dosing particles are free from cleaning agents.
  • Said treatments are optimally performed by mixing in said dosing particles during the rinse cycle of a cleaning operation, rather than at an earlier stage in the process.
  • Suitable examples of such processes could include the release of an antimicrobial agent or other sterilising agent onto a fabric surface for sterilisation purposes or dosing with an optical brightening agent, an anti-redeposition agent, a fragrance, or a dye transfer inhibition agent.
  • the invention also envisages a method by which the dosing particles release an antimicrobial agent within the washing apparatus internal water storage areas or conduits during idle periods between wash cycles, thereby enhancing the hygiene of the apparatus itself.
  • the method according to the second aspect of the invention typically involves the cleaning of a soiled substrate and comprises, in sequence, the steps of:
  • the method of the second aspect of the present invention may be used for either small or large scale batchwise processes. It also finds application in both domestic and industrial cleaning processes.
  • the method of the invention may be applied to the cleaning of any of a wide range of substrates including, for example, plastics materials, leather, paper, cardboard, metal, glass or wood.
  • said method is principally applied to the cleaning of substrates comprising textile fibres and fabrics, and has been shown to be particularly successful in achieving efficient cleaning of textile fabrics which may, for example, comprise either natural fibres, such as cotton, or man-made and synthetic textile fibres, for example nylon 6,6, polyester, cellulose acetate, or fibre blends thereof.
  • the treatment in the method according to the second aspect of the present invention can comprise a rinse cycle.
  • the treatment typically comprises rinsing the substrate in the presence of the dosing particles and cleaning particles.
  • the rinsing typically comprises the addition of water which is subsequently or simultaneously removed.
  • This embodiment of the method according to the second aspect of the present invention is especially suitable when the dosing particles comprise a bleach compound and/or a bleach activator and/or an antimicrobial agent as the releasable material.
  • the method can comprise: (i) washing the substrate in a wash formulation which comprises water and one or more cleaning agents (such as enzymes) either in the presence or absence of the cleaning particles; (ii) optionally rinsing the substrate (typically with water) and/or extracting the water from the substrate; (iii) adding cleaning particles if not already present from step (i); and (iv) treating the substrate in the presence of the cleaning particles and the dosing particles.
  • the treatment step typically comprises agitation, more typically tumbling.
  • step (iv) is performed using a formulation which is free of any enzymes.
  • step (i) is performed using a formulation which comprises no bleach compound and/or no bleach activator.
  • the wash formulation in step (i) comprises one or more enzymes.
  • This method is especially suitable when the dosing particles comprise a bleach compound and/or a bleach activator and/or an antimicrobial agent as the releasable material. This embodiment has the advantage that a better combination of cleaning and sterilisation can be achieved.
  • This Example shows how the use of single-use core-shell dosing particles in combination with cleaning beads reduces the amount of red dye transferred to a white cloth from a dye eluting material in a laundry "bead cleaning" process.
  • core-shell dosing particles are used in conjunction with polymeric cleaning beads; specifically, the cleaning beads consisted of nylon 6,6 filled with 40% barium sulphate (Technyl XA 1493). These were cut to an ellipsoid shape (-4.5 x 3.5 x 3.2 mm) by under-water die face cutting. The material was supplied by Solvay Chemicals, Lyon France.
  • Powders of a) chitosan (ChitoClear 40400, from Primex EHF, Siglufjord, Iceland), b) chitosan (from Sigma-Aldrich, Gillingham, UK, product number 448869) and c) cross- linked polyvinyl pyrrolidone (PVP) (Disintex 2000, Ashlands Speciality Ingredients, Wayne, NJ 07470, USA) were compressed in a Casburt tableting machine. The diameter of the tableting die was 10 mm. Tablet thickness values were measured with a Copley TBF100 device. The physical properties of the pellets are listed in Table 1 ; these tablets form the "core" of the core-shell pellets with cores of chitosan or PVP.
  • Calcium bentonite in pelletised form (“Mikolit B") (obtained from Marton Geotechnical Services Ltd., Geotechnical Centre, Rougham, Bury St Edmunds, Suffolk, UK) was also used. This material formed the “core” of the calcium bentonite particle.
  • Tablets were coated with a shell of polyvinyl alcohol (Elvanol 85-82, Du Pont, Wilmington, DE, USA) by pouring an 1 1 % solution of Elvanol 85-82 through a sieve containing the tablets. Tablets were then dried in an oven at 65°C.
  • polyvinyl alcohol Elvanol 85-82, Du Pont, Wilmington, DE, USA
  • the source of red dye was two new, unwashed red tee shirts (Fruit of the Loom, size XXL).
  • the ballast consisted of used polyester clean-room suits.
  • the weight of the washload is defined as the weight of the tee shirts plus the weight of the ballast, and this was kept at 1.4 kg. In all cases the weight ratio of Technyl cleaning beads to washload was 2: 1.
  • the items for each wash load were placed in a net mesh bag; beads and/or dosing paricles were mixed thoroughly with the fabric materials.
  • the fabric materials were inserted into the mesh bag in layers to disperse items evenly throughout the mesh bag, which was sealed by tying.
  • the mesh bag was washed in a Beko domestic washing machine using a 40°C cotton cycle with 11.2 g of Pack I detergent available from Xeros Ltd. (a proprietary formulation comprising surfactants and enzymes).
  • the spin speed set was 1200 rpm.
  • the ratio (by weight) of wash load to Xeros Pack I detergent was therefore approximately 8 g/kg.
  • Figure 1 also shows that the core-shell dosing particles compare very well with the commercial dye catching sheet, where the reduction of a* (compared to the experiment without dosing particles) was approximately 2.3.
  • Figure 2 provides an illustration of the use of core-shell dosing particles on a white-grey scale. It is apparent that particles with cores of PVP and chitosan both have the effect of brightening the fabric, which is a desirable effect.
  • FIG 3 the effect of dosing particles on b* is illustrated.
  • the b* parameter is indicative of the blue-yellow balance of the colour; a change to a more positive b* means an increasingly more yellow colour, while a change to more negative b* means an increasingly blue colour.
  • Figure 3 shows that dosing particles with a calcium bentonite core impart a yellow colour to the white fabric compared to Technyl cleaning beads alone; however, dosing particles with cores of PVP and chitosan do not cause a significant yellowing effect. In fact, the use of PVP and chitosan particles bring the value of b* closer to that of virgin cloth (1.45 ⁇ 0.05) than does the use of cleaning beads alone.
  • Values of DE are presented in Figure 4. Values of DE provide a measure of the overall change in appearance of cloth compared to unwashed, virgin cloth. The lower the value of DE, the closer the appearance of the material is to a reference material (in this case, virgin cloth). Figure 4 shows that the use of chitosan or PVP particles in conjunction with Technyl cleaning beads significantly reduces DE values when compared to the case of washing with Technyl cleaning beads alone.
  • a value of DE is simply an overall indication of the changes in the three parameters, L*, a* and b*, compared to the virgin cloth; it does not take into account whether a change in any of these individual parameters in desirable or not.
  • L* the increase in L* is desirable (brighter cloth); nevertheless, this desirable change in L* leads to an increase in the value of DE. Consequently, the appearance of the final cloths washed in the presence of chitosan and PVP dosing particles is actually found to be better than would be suggested by the values of DE in Figure 4.
  • Runs A and B therefore simulated conventional washes (without cleaning beads) whilst Run C was a bead cleaning wash.
  • Table 6 shows that the a* value for PVP particles is 1.4 units below that for PVP powder, i.e. there is less red dye transfer with the particle than with the powder.
  • the value of a* is 2.24 lower for chitosan in particle form than when in powder form, again showing there is less red dye transfer with the particle than with the powder.
  • An additional benefit of dosing particles of precise weight is that they facilitate the introduction of precise levels of dosing materials to the wash (thereby reducing wastage) in a form which is highly convenient to the end-user.
  • This Example shows how the original quantity of source of vagrant dye affects degree of dye transfer in the presence of dye transfer inhibiting core-shell particles. Specifically, the amount of dye transferred to a cloth is lowered when there is less vagrant dye in the wash.
  • the wash protocol was exactly as described in Example 1 , with the cleaning beads, except that the weight of dye eluting red tee shirt material was varied; additional ballast was added to keep the weight of the washload constant at 1.4k g. 2.5 g and 10 g of core-shell particles with Chitosan cores were used in this example. A 1.4 kg washload was used and the temperature of treatment was 40°C.
  • a control was carried out in which chitosan and the dye eluting tee shirts were omitted, the washload consisting entirely of 1.4 kg of polyester ballast.
  • the human eye can only detect differences larger than 1 unit, which means that the chitosan dosing particles have reduced dye transfer to the extent that the human eye cannot detect the difference between the cloth washed with a dye source and a cloth washed in detergent alone.
  • This Example shows how the use of single-use core-shell dosing particles in combination with cleaning beads kills bacteria in a laundry "bead cleaning" process.
  • the efficacy of disinfection was assessed by washing cloths inoculated with bacteria in a bead washing machine such as that described in WO-A-201 1/098815, and comparing the number of bacterial colony forming units (cfu) remaining per cloth after washing with the number of cfu per cloth on an inoculated unwashed cloth.
  • core-shell dosing particles were used in conjunction with polymeric cleaning beads; specifically, the cleaning beads consisted of nylon 6,6 filled with 40% barium sulphate (Technyl XA 1493). These were cut to an ellipsoid shape (-4.5 x 3.5 x 3.2 mm) by under-water die face cutting. The material was supplied by Solvay Chemicals, Lyon France. The cleaning beads were used in a Xeros washing machine as described in WO-A-2011/098815.
  • the powder particles of sodium percarbonate were supplied by the manufacturer, Solvay, coated with a protective surface layer.
  • the composition of the formulation is shown in Table 9. The diameter of the tableting die was 19 mm and the weight of each tablet was 2.5 g.
  • Powders of a) TAED (Mykon B610) and b) polyethylene glycol (PEG 600) were blended and compressed into tablets by Stonehouse Tableting.
  • the composition of the formulation is shown in Table 10.
  • the diameter of the tableting die was 19 mm and the weight of each tablet was 2.5 g.
  • the shell of the particles was formed from polyethylene glycol (PEG 2000, Merck, Hohenbrunn, Germany). This was achieved by dipping tablet cores in a 2% (by weight) solution of PEG 2000 in ethanol at room temperature, and allowing this to dry in air at room temperature.
  • PEG 2000 polyethylene glycol
  • the rationale for using an ethanol solution of PEG 2000 rather than an aqueous solution was that the cores dissolved very rapidly on contact with water, thereby precluding the use of aqueous solution for shell formation; the use of an ethanol solution of PEG 2000 permitted the formation of the shell without compromise of the core material.
  • the PEG formed a water soluble shell around the core.
  • PEG 2000 was chosen as the shell material because it is soluble in both ethanol (for pellet preparation) and water (for dissolution in use in a washing machine).
  • the bacteria used are listed in Table 11 ; the American Type Culture Collection (ATTC) identification codes for the bacterial strains are also shown. Bacteria ATCC number
  • Washing was carried out in a Xeros bead cleaning washing machine as described in WO-A-201 1/098815 using one of two wash programs.
  • Controls for assessment of disinfection efficacy were unwashed inoculated cloths, inoculated at the same time as the test cloths and kept under the same conditions as test cloths. New controls were prepared every day of testing and comparison of test samples were with respect to the controls prepared that day.
  • Hygiene promoting agents were added to the machine in the following forms:
  • Table 12 provides the details of the wash temperature, specific dosing particles (or other hygiene promoting agents) and point of introduction of the hygiene promoting agents used for each test. Test Hygiene promoting agents When Weight Weight Wash
  • inoculated cloths were recovered from the wash-load, kept in sterile plastic bags (one cloth per bag) and returned the same day to Microbiological Consultant Services (MCS) for analysis.
  • MCS Microbiological Consultant Services
  • E coli - Pour plates in TBX agar. Incubation at 44°C for 24 hours.
  • Test cloth ⁇ 10 1.3 x 10 3 8.0 x 10 2 ⁇ 10 3.6 x 10 3 average
  • Test cloth ⁇ 10 ⁇ 10 ⁇ 10 2.1 x 10 4 ⁇ 10 average
  • Test 1.4 shows that if only SPC containing particles were used without TAED, the reduction in bacterial levels were only slightly larger than for the control (Test C1 , Table 14-L), showing that, at 20°C, both SPC and TAED are required for effective antimicrobial effect.
  • Test C4 (Table 14-0), in which 7.5 g of Formulation "A" was used in the absence of nylon cleaning beads, provided similar hygiene levels as Test 1.1 (Table 14-A), which was conducted in the presence of the nylon cleaning particles. This shows there is no reduction in the efficacy of the dosing particles by using them in conjunction with the nylon cleaning beads but, by using dosing particles in conjunction with cleaning beads, the benefits of improved low temperature hygiene and low temperature cleaning can be combined.
  • This Example shows how the use of single-use core-shell dosing particles comprising a quaternary ammonium compound (“Cetrimide” (CTAB)) in combination with cleaning beads kills bacteria in a laundry "bead cleaning” process using the procedure described above in Example 4.
  • Cetrimide quaternary ammonium compound
  • Table 15 shows that use of core-shell particles with a core of CTAB in conjunction with solid cleaning particles reduce the level of Staphylococcus Aureus, Pseudomonas Aeruginosa and Klebsiella Pneumoniae by log 2, log 1 and log 1 , respectively.
  • CTAB was not effective.
  • This Example shows how the use of single-use core-shell dosing particles in combination with cleaning beads inhibits re-deposition of removed soil onto fabric in a laundry "bead cleaning" process. This has the desirable effect of greatly reducing the "greying" of fabric during washing.
  • core-shell dosing particles are used in conjunction with polymeric cleaning beads; specifically, the cleaning beads consisted of nylon 6,6 filled with 40% barium sulphate (Technyl XA 1493). These were cut to an ellipsoid shape (-4.5 x 3.5 x 3.2 mm) by under-water die face cutting. The material was supplied by Solvay Chemicals, Lyon France.
  • CMC carboxy methyl cellulose
  • HPMC hydroxyl propyl methyl cellulose
  • a washload consisting of 4 kg of used polyester clean-room suits was used.
  • One and a half sebum sheets one sheet measuring 23 x 61 cm) (Product code SBL 2004, WFK Testgewebe GmbH, D-41379, Germany) and four cotton cloths (17 x 28 cm) (Whaley's (Bradford) Ltd., Bradford UK) were added to the washload.
  • the source of soil was a "greying donor" swatch (Article 10991 , from WFK Testgewebe GmbH, Bruggen, Germany). In all cases 2 kg of Technyl cleaning beads were used; the weight ratio of Technyl cleaning beads to washload was therefore 1 :2. The temperature of wash treatment was 40°C.
  • the mesh bag was washed in a Beko domestic washing machine using a 40°C cotton cycle with 32 g of Xeros Pack I detergent available from Xeros Ltd. (a proprietary formulation comprising surfactants and enzymes).
  • the spin speed set was 1200 rpm.
  • the ratio (by weight) of wash load to Xeros Pack I detergent was therefore approximately 8 g/kg.
  • Figure 7 shows how the use of core-shell dosing particles with cores of CMC affects the value of L* over ten repeated wash cycles, a) without core-shell dosing particles, b) with 2.5 g CMC dosing particles, and c) with 5 g CMC dosing particles (new dosing particles added to each wash).
  • Run A was therefore a simulated conventional wash (without cleaning beads), whilst Run B was a bead cleaning wash.

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PCT/GB2014/052079 2013-07-08 2014-07-08 New cleaning formulation and method WO2015004444A1 (en)

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CN106494804A (zh) * 2016-10-31 2017-03-15 广西大学 一种垃圾箱
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WO2017218772A1 (en) * 2016-06-17 2017-12-21 The Procter & Gamble Company Delayed-release particles
US10081900B2 (en) 2013-11-08 2018-09-25 Xeros Limited Cleaning method including use of solid particles
US10494590B2 (en) 2012-07-06 2019-12-03 Xeros Limited Cleaning material
WO2020012027A1 (en) 2018-07-13 2020-01-16 Xeros Limited Apparatus and method for treating a substrate with solid particles
WO2020012026A1 (en) 2018-07-13 2020-01-16 Xeros Limited Apparatus and method for treating a substrate with solid particles
WO2020012024A1 (en) 2018-07-13 2020-01-16 Xeros Limited Apparatus and method for treating a substrate with solid particles
WO2020064830A1 (en) 2018-09-26 2020-04-02 Xeros Limited Apparatus and method for treating a substrate with solid particles
US10865364B2 (en) 2015-07-29 2020-12-15 Basf Se Cleaning particles and their use
WO2021032986A1 (en) 2019-08-21 2021-02-25 Xeros Limited New filter, filter unit, treatment apparatus, method and use
WO2021234184A1 (es) * 2020-05-20 2021-11-25 Ancor Tecnológica Canaria, S.L. Composición desinfectante y protectora para textiles o similares
WO2022063939A1 (de) * 2020-09-23 2022-03-31 MWK Bionik GmbH Mehrkomponenten-zusammensetzung zur oberflächenbehandlung
US11414633B2 (en) 2015-07-29 2022-08-16 Xeros Limited Cleaning method, apparatus and use
EP4066916A2 (en) 2017-12-19 2022-10-05 Xeros Limited Filter for a treatment apparatus
EP4177391A1 (en) 2017-03-24 2023-05-10 Xeros Limited Apparatus and method for the treatment of a substrate with a multiplicity of solid particles

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US9803307B2 (en) 2011-01-14 2017-10-31 Xeros Limited Cleaning method
US10494590B2 (en) 2012-07-06 2019-12-03 Xeros Limited Cleaning material
US10081900B2 (en) 2013-11-08 2018-09-25 Xeros Limited Cleaning method including use of solid particles
WO2016087834A1 (en) * 2014-12-01 2016-06-09 Xeros Limited New cleaning method, apparatus and use
AU2015356816B2 (en) * 2014-12-01 2019-10-10 Xeros Limited New cleaning method, apparatus and use
US10781404B2 (en) 2014-12-01 2020-09-22 Xeros Limited Cleaning method, apparatus and use
US20170267949A1 (en) * 2014-12-01 2017-09-21 Xeros Limited New cleaning method, apparatus and use
CN107001988A (zh) * 2014-12-01 2017-08-01 塞罗斯有限公司 新的清洁方法、装置及应用
US11414633B2 (en) 2015-07-29 2022-08-16 Xeros Limited Cleaning method, apparatus and use
US10865364B2 (en) 2015-07-29 2020-12-15 Basf Se Cleaning particles and their use
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JP2019515080A (ja) * 2016-04-26 2019-06-06 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 熱可塑性ポリアミド粒子
CN109415507B (zh) * 2016-04-26 2022-03-08 巴斯夫欧洲公司 热塑性聚酰胺颗粒
WO2017186677A1 (en) * 2016-04-26 2017-11-02 Basf Se Thermoplastic polyamide particles
US11401382B2 (en) 2016-04-26 2022-08-02 Basf Se Thermoplastic polyamide particles
WO2017218772A1 (en) * 2016-06-17 2017-12-21 The Procter & Gamble Company Delayed-release particles
CN106494804A (zh) * 2016-10-31 2017-03-15 广西大学 一种垃圾箱
EP4177391A1 (en) 2017-03-24 2023-05-10 Xeros Limited Apparatus and method for the treatment of a substrate with a multiplicity of solid particles
EP4066916A2 (en) 2017-12-19 2022-10-05 Xeros Limited Filter for a treatment apparatus
WO2020012027A1 (en) 2018-07-13 2020-01-16 Xeros Limited Apparatus and method for treating a substrate with solid particles
WO2020012024A1 (en) 2018-07-13 2020-01-16 Xeros Limited Apparatus and method for treating a substrate with solid particles
WO2020012026A1 (en) 2018-07-13 2020-01-16 Xeros Limited Apparatus and method for treating a substrate with solid particles
WO2020064830A1 (en) 2018-09-26 2020-04-02 Xeros Limited Apparatus and method for treating a substrate with solid particles
WO2021032986A1 (en) 2019-08-21 2021-02-25 Xeros Limited New filter, filter unit, treatment apparatus, method and use
WO2021234184A1 (es) * 2020-05-20 2021-11-25 Ancor Tecnológica Canaria, S.L. Composición desinfectante y protectora para textiles o similares
WO2022063939A1 (de) * 2020-09-23 2022-03-31 MWK Bionik GmbH Mehrkomponenten-zusammensetzung zur oberflächenbehandlung

Also Published As

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CN105378048B (zh) 2019-08-16
KR20160030290A (ko) 2016-03-16
EP3019585B1 (en) 2019-09-04
TW201508060A (zh) 2015-03-01
EP3019585A1 (en) 2016-05-18
GB201312189D0 (en) 2013-08-21
CN105378048A (zh) 2016-03-02

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